Electrorefining

Electrorefining has its ftmdamentals based on the principles of electrochemical kinetics. The anodes are artificially oxidized by loosing electrons and freeing cations, which migrate towards the cathode surfaces through the solution under the influence of an applied current in opposite direction. As a result, the cations AT combine with electrons to form reduction reactions. This is the source of electrolytic metal deposition, which in turn, becomes adhered as a layer on the cathode surfaces. This layer increases in thickness as electrolysis proceeds up to an extend determined by experimentation or industrial practice. The refining process can be represent by a reversible electrochemical reactions of the form 

In an electrorefining process, the anode is the impure metal and the impurities must be lost during the passage of the metal from the anode to the cathode during electrolysis, i.e. the electrode reactions are, at the anode 

Electrorefining is a much more common process than electrowinning and such plants occur throughout the world on scales between 1000—100 000 ton yr . Usually they are part of a larger operation to separate and recover pure metals from both scrap and primary ores. Therefore, the process must be designed to handle a variable-quality metal feed and lead to a concentration of all the metals present in a form which can be treated further. Electrorefining leads to metal of the highest purity. 

The conditions used for the refining of five metals are summarized in Table 4.3. 

The electrolyte and other conditions must be selected so that both the anodic dissolution and the deposition of the metal occur with high efficiency while none of the impurity metals can transfer from the anode to the cathode. Certainly there must be no passivation of the anode (see Chapter 9) and the objective is to obtain a good-quality, often highly crystalline, deposit at the cathode. Where necessary, additives are added to the electrolyte to enforce the correct behaviour at both electrodes. Chloride ion is a common addition to enhance the dissolution process and, where essential, organic additives are used to modify the cathode deposit. Since, however, organic compounds can be occluded to some extent and reduce the purity of the metal, their use is avoided when possible. 

The process for electrorefining copper is typical of those carried out in aqueous solution. The electrolyte is copper sulphate (0.7 M) and sulphuric acid (2 M) and the way in which the purification of the copper occurs can be seen by considering the metals hkely to be found as impurities  

Metal J/mAcm -Cell voltage/V T/ C Slime Solution 

Au and Pt are more noble than copper and therefore will not dissolve anodically. They will be found as metals in the anode slime. 

---

The purification of the galHum salt solutions is carried out by solvent extraction and/or by ion exchange. The most effective extractants are dialkyl-phosphates in sulfate medium and ethers, ketones (qv), alcohols, and trialkyl-phosphates in chloride medium. Electrorefining, ie, anodic dissolution and simultaneous cathodic deposition, is also used to purify metallic galHum. 

Electrometallurgy. A term covering the various electrical processes for the working of metals, eg, electro deposition, electrorefining and electro winning, and operations in electric furnaces. 

Electrorefining. Electrolytic refining is a purification process in which an impure metal anode is dissolved electrochemicaHy in a solution of a salt of the metal to be refined, and then recovered as a pure cathodic deposit. Electrorefining is a more efficient purification process than other chemical methods because of its selectivity. In particular, for metals such as copper, silver, gold, and lead, which exhibit Htfle irreversibHity, the operating electrode potential is close to the reversible potential, and a sharp separation can be accompHshed, both at the anode where more noble metals do not dissolve and at the cathode where more active metals do not deposit. 

Normal ceU voltages are ca 0.2 V. The power consumption is correspondingly very smaH, and electrorefining is much less sensitive to the cost of electric power than other electrometaHurgical processes. When a diaphragm is used to separate the anodic and cathodic solutions, the ceU voltage increases up to ca 1.2 V, and the power consumption rises accordingly. 

Other Meta.Is, Although most cobalt is refined by chemical methods, some is electrorefined. Lead and tin are fire refined, but a better removal of impurities is achieved by electrorefining. Very high purity lead is produced by an electrochemical process using a fluosiUcate electrolyte. A sulfate bath is used for purifying tin. Silver is produced mainly by electrorefining in a nitrate electrolyte, and gold is refined by chemical methods or by electrolysis in a chloride bath. 

The electrorefining of many metals can be carried out using molten salt electrolytes, but these processes are usually expensive and have found Httie commercial use in spite of possible technical advantages. The only appHcation on an industrial scale is the electrorefining of aluminum by the three-layer process. The density of the molten salt electrolyte is adjusted so that a pure molten aluminum cathode floats on the electrolyte, which in turn floats on the impure anode consisting of a molten copper—aluminum alloy. The process is used to manufacture high purity aluminum. 

Preparation of Plutonium Metal from Fluorides. Plutonium fluoride, PuF or PuF, is reduced to the metal with calcium (31). Although the reactions of Ca with both fluorides are exothermic, iodine is added to provide additional heat. The thermodynamics of the process have been described (133). The purity of production-grade Pu metal by this method is ca 99.87 wt % (134). Metal of greater than 99.99 wt % purity can be produced by electrorefining, which is appHcable for Pu alloys as well as to purify Pu metal. The electrorefining has been conducted at 740°C in a NaCl—KCl electrolyte containing PuCl [13569-62-5], PuF, or PuF. Processing was done routinely on a 4-kg Pu batch basis (135). 

A more recently developed pyrometaHurgical process is that of the proposed integral fast reactor, which would use metallic fuel (U—Pu—Zr alloy) and a molten salt electrorefiner as follows ... 

Manufacture and Recovery. Electrolytic copper refinery slimes are the principal source of selenium and its sister element, tellurium, atomic numbers 34 and 52, respectively. Electrolytic copper refinery slimes are those constituents in the copper anode which are not solubilized during the refining process and ultimately accumulate in the bottom of the electrorefining tank. These slimes are periodically recovered and processed for their metal values. Slimes generated by the refining of primary copper, copper produced from ores and concentrates, generally contain from 5—25% selenium and 2—10% tellurium. 

An electrorefining plant may operate with either an acid or an alkaline bath. The acid bath contains stannous sulfate, cresolsulfonic or phenolsulfonic acids (to retard the oxidation of the stannous tin in the solution), and free sulfuric acid with P-naphthol and glue as addition agents to prevent tree-like deposits on the cathode which may short-circuit the cells. The concentration of these addition agents must be carefliUy controlled. The acid electrolyte operates at room temperature with a current density of ca 86—108 A/m, cell voltage of 0.3 V, and an efficiency of 85%. Anodes (95 wt % tin) have a life of 21 d, whereas the cathode sheets have a life of 7 d. Anode slimes may be a problem if the lead content of the anodes is high the anodes are removed at frequent intervals and scmbbed with revolving bmshes to remove the slime (7). 

Electron-beam melting of zirconium has been used to remove the more volatile impurities such as iron, but the relatively high volatiUty of zirconium precludes effective purification. Electrorefining is fused-salt baths (77,78) and purification by d-c electrotransport (79) have been demonstrated but are not in commercial use. 

Monovalent Halides. Zirconium monochloride [14989-34-5], ZrCl, was discovered during electrorefining studies of zirconium in a SrCl2—NaCl—ZrCl4 melt intended to produce pure ductile hafnium-depleted zirconium from cmde zirconium anodes (180—181). The monochloride is also called Zirklor. It is obtained as black flakes with a graphite sHp-plane behavior and was proposed as a lubricant (182,183). 

Electrolytic Processes. The electrolytic procedures for both electrowinning and electrorefining beryUium have primarily involved electrolysis of the beryUium chloride [7787-47-5], BeCl2, in a variety of fused-salt baths. The chloride readUy hydrolyzes making the use of dry methods mandatory for its preparation (see Beryllium compounds). For both ecological and economic reasons there is no electrolyticaUy derived beryUium avaUable in the market-place. 

Commercial electrorefining of beryUium has been carried out to obtain a purer metal than the magnesium-reduced beryUium. The most notable purification obtained with respect to iron was specified as 300 ppm maximum, and typicaUy between 100 and 200 ppm Fe as contrasted with the 500—1000 ppm, found in the Mg-reduced beryUium metal. There is, however, no metaUurgical advantage to having a metal of improved purity. 

Fire Refining. The impurities in bhster copper obtained from converters must be reduced before the bUster can be fabricated or cast into anodes to be electrolyticaHy refined. High sulfur and oxygen levels result in excessive gas evolution during casting and uneven anode surfaces. Such anodes result in low current efficiencies and uneven cathode deposits with excessive impurities. Fite refining is essential whether the copper is to be marketed directly or electrorefined. 

Fite refining adjusts the sulfur and oxygen levels in the bhster copper and removes impurities as slag or volatile products. The fire-refined copper is sold for fabrication into end products, provided that the chemistry permits product specifications to be met. Some impurities, such as selenium and nickel, are not sufficiently removed by fire refining. If these impurities are detrimental to fabrication or end use, the copper must be electrorefined. Other impurities, such as gold, silver, selenium, and tellurium, are only recovered via electrorefining. Virtually all copper is electrorefined. 

If the fire-refined copper is to be cast into anodes for electrorefining, the oxygen content of the copper is lowered to 0.05—0.2%. If the copper is to be sold directly for fabrication, the oxygen level is adjusted to 0.03—0.05%, which is the range for tough-pitch copper. The principal reactions of fire refining are... 

Electrodeposition. Electro deposition, the most important of the unit processes in electrorefining, is performed in lead- or plastic-lined concrete cells or, more recently, in polymer—concrete electrolytic cells. A refinery having an aimual production of 175,000 t might have as many as 1250 cells in the tank house. The cells are multiply coimected such that anodes and cathodes are placed alternately and coimected in parallel. Each cell is a separate unit and electrically coimected to adjacent cells by a bus bar. 

The tank house is divided into commercial and stripper sections. In the latter, one-day deposits are prepared by electrorefining anode copper onto oiled copper, stainless steel, or titanium blanks. These copper sheets are stripped from the blanks and fabricated into starter sheets for the commercial sections as starting cathodes. After 9—15 days, depending on the tank house, hill-term cathodes are pulled and washed and either sent to the casting department or sold direcdy. 

The total impurity content of anodes used in electrorefining is usually less than 1%, of which oxygen is the highest, ranging from ca 0.1 to 0.25%. This oxygen gives copper(I) oxide, which then reacts with the acid of the electrolyte... 

Although some changes occur in the melting furnace, cathode impurities are usually reflected directly in the final quaUty of electrorefined copper. It is commonly accepted that armealabiUty of copper is unfavorably affected by teUurium, selenium, bismuth, antimony, and arsenic, in decreasing order of adverse effect. Silver in cathodes represents a nonrecoverable loss of silver to the refiner. If the copper content of electrolyte is maintained at the normal level of 40—50 g/L, and the appropriate ratio of arsenic to antimony and bismuth (29) is present, these elements do not codeposit on the cathode. 

In electro winning, the cathode reaction is the same as for electrorefining (see eq. 31). However, because of the use of insoluble anodes, oxygen is released at the anode. 

In contrast with electrorefining, there is a minimum cell voltage of ca 1.67 V, below which there is no appreciable current flow. Hence, the energy yield is only ca 0.3 kg of copper per kilowatt hour, as contrasted with about 3 kg/kWh for electrorefining. 

Calcining, sintering or smelting of nickel copper matte or acid leaching or electrorefining of roasted matte Coal soots, coal tar, pitch and coal tar fumes Hardwood dusts... 

Air emissions for processes with few controls may be of the order of 30 kilograms lead or zinc per metric ton (kg/t) of lead or zinc produced. The presence of metals in vapor form is dependent on temperature. Leaching processes will generate acid vapors, while refining processes result in products of incomplete combustion (PICs). Emissions of arsine, chlorine, and hydrogen chloride vapors and acid mists are associated with electrorefining. 

In the field of electrowinning and electrorefining of metals, titanium has an advantage as a cathode, upon which copper particularly can be deposited with finely balanced adhesion that allows the electrodeposited metal to strip easily when required. Titanium anodes are also being employed as a replacement for lead or graphite in the production of electrolytic manganese dioxide. 

---